A Metallofullerene Electron Donor that Powers an Efficient Spin Flip in a Linear Electron Donor–Acceptor Conjugate

Abstract

The dream target of artificial photosynthesis is the realization of long-lived radical ion pair states that power catalytic centers and, consequently, the production of solar fuels. Notably, magnetic field effects, especially internal magnetic field effects, are rarely employed in this context. Here, we report on a linear Lu3N@Ih-C80-PDI electron donor-acceptor conjugate, in which the presence of the Lu3N cluster exerts an appreciable electron nuclear hyperfine coupling on the charge transfer dynamics. As such, a fairly efficient radical ion pair intersystem crossing converts the initially formed singlet radical ion pair state, (1)[(Lu3N@Ih-C80)(•+)-PDI(•-)], to the corresponding triplet radical ion pair state, (3)[(Lu3N@Ih-C80)(•+)-PDI(•-)]. Most notably, the radical ion pair state lifetime of the latter is nearly 1000 times longer than that of the former.